Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/0883—Arsenides; Nitrides; Phosphides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides

Definitions

• the invention belongs to the field of luminescent materials, and is specifically a method for preparing a nitride phosphor containing an inorganic luminescent material and a nitride phosphor prepared by the method. Background technique
• LEDs are characterized by high efficiency, energy saving, safety and long life. There are two ways to implement LED white light. The first method is to use red, yellow and/or blue LED chips alone, and the second method is to use ultraviolet or blue light chips in combination with phosphors.
• the white light thus produced is poor in color development.
• the current common method is to use a blue chip and two phosphors, that is, a combination of yellow and red phosphors, or use a blue chip to combine with three phosphors, namely yellow, red and green phosphors.
• the known orange-red-red phosphors have a silicate structure, a nitride structure and an oxynitride structure. Silicate phosphors are unstable to humidity and cause certain limitations on LED outdoor applications.
• the nitrogen (oxygen) phosphor is structurally stable and is currently a superior phosphor.
• (Sr,Ca) 2 Si 5 N 8 Eu red phosphor (EP 99123747.0 ) issued by Osram
• (Sr, Ca)SiAlN 3 Eu red phosphor disclosed by Nichia (US7476337) and Mitsubishi (200680017011 and 200780001497) .
• the present invention provides a simple method for preparing a nitride phosphor using a cheap and readily available raw material, and the nitride phosphor obtained by the method has good particle size uniformity and compositional consistency.
• a first object of the present invention is to provide a method of preparing a nitride phosphor, the method comprising the steps of: (a) a raw material mixing step in which a first raw material, a second raw material, a third raw material, and a flux, or The first raw material, the third raw material and the flux, or the first raw material, the Si 3 N 4 , the third raw material and the flux, or the first raw material, the second raw material, the third raw material, the Si 3 N 4 and the auxiliary The flux is added to the dispersant and uniformly mixed; (b) a drying step in which the uniformly mixed raw material is dried; (c) a heating reduction step in which the dried mixed raw material is heated in a reducing gas.
• the first raw material is an oxide, a halide or a carbonate of the element IA, ⁇ , IB or a lanthanum element of the periodic table, or a mixture of two or more thereof .
• the first raw material is an oxide or carbonate of Li, Mg, Ca, Sr, Ba, Be, Zn, Cd or Hg, or two or more of them a mixture; preferably one or both of Ca, Sr, Ba;
• the second raw material is an oxide, a halide or a carbonate of the element ⁇ , IVA, VA, IVB or VB of the periodic table, or the second raw material is an oxide, a halide or a carbon of Sc or Y An acid salt, or a mixture of two or more of them.
• the second raw material is an oxide of C, Ge, Sn, Ti, Hf, Mo, Zr, Al, W, Bi, B, Sc, Ga, In or Y, or a mixture of two or more thereof, More preferably, Al.
• the third raw material is an oxide, a halide or a carbonate of a lanthanoid element, or a mixture of two or more kinds thereof.
• the third raw material is an oxide or chloride of Eu, Ce, Mn, Sm, La, Pr or Tb, or a mixture of two or more thereof, more preferably Eu.
• the molar equivalent ratio of the first raw material, the second raw material, the third raw material and the Si 3 N 4 added is a: b: c: d, wherein a is 0.5 To 0.998, b is 0 to 1.5, c is 0.002 to 0.5, and d is 0 to 1;
• the flux is NH 4 C1, NH 4 F or a halide containing the same metal element as the metal element in the first raw material, or a mixture of two or more of them.
• the flux is used in an amount of from 0.05% to 10%, preferably from 0.05% to 5%, more preferably from 0.05% to 2%, still more preferably from 0.075 to 1.5%, most preferably from 0.75 to 1% by weight of the total of the raw materials, as the flux
• the dosage is less than 0.05%, the effect of the flux is not obvious, and the firing temperature and performance of the sample are not significantly improved.
• the amount of the flux exceeds 10%, the luminescence property of the sample is lowered.
• the dispersing agent used in the raw material mixing step is any one of water or an organic solvent or a mixture of two or more kinds thereof.
• the organic solvent used in the raw material mixing step is any one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, diethyl ether, acetone, methyl ethyl ketone, benzene or toluene, or among them A mixture of two or more.
• the raw gas in the heating and reduction step is a mixed gas of CH 4 /NH 3 .
• the synthesis temperature in the heating reduction step is 1200 ° C to 1800 ° C, preferably 1300 ° C to 1800 ° C, more preferably 1400 ° C to 1750 ° C, most preferably 1600 ° C to 1700 ° C, when the temperature When the temperature is lower than 1200 ° C, the reaction does not proceed smoothly. When the temperature is higher than 1800 ° C, the adverse effect of excessive sintering of the sample occurs, and energy is wasted.
• the reaction pressure in the heating reduction step is from 0.1 to 1.0 MPa, preferably from 0.3 to 0.9 MPa, more preferably from 0.5 to 0.8 MPa, and most preferably from 0.6 to 0.7 MPa.
• the pressure is lower than O.lMPa, the doping degree of the reaction activator is low.
• the pressure is higher than IMPa, the required reaction temperature is high, and the equipment requires a special pressure-resistant design, which increases the cost.
• the heating reduction step is carried out for a period of from 2 hours to 12 hours, preferably from 2 to 10 hours, more preferably from 4 to 10 hours, and most preferably from 4 to 8 hours.
• the duration is shorter than 2 hours, the sample reaction is incomplete, and in the case where the duration is longer than 12 hours, the sample particles are excessively grown.
• a second object of the present invention is to provide a nitride phosphor, the nitride phosphor There is a chemical formula I w II x Si y (N 3 _ z O z ) m w .
• the nitride phosphor has an average particle diameter of from 4 ⁇ m to 15 ⁇ m, preferably from 5 ⁇ m to 12 ⁇ m, more preferably from 5 ⁇ m to ⁇ , still more preferably from 5 ⁇ m to 9 ⁇ m, and most preferably from 6 ⁇ m to 9 ⁇ m.
• average particle diameter is less than 5 ⁇ m, the quantum efficiency of the sample is low.
• average particle diameter is larger than 15 ⁇ m, the particles are too large, which is disadvantageous for the packaging process.
• D50/(D90-D10) 1.0 to 2.0, preferably 1.3 to 2.0, more preferably 1.4 to 2.0, most preferably 1.5 to 1.9.
• the particle size distribution is greater than 2.5, the consistency of the powder is poor, which is not conducive to the packaging process.
• I in the chemical formula is IA, II A, IB or a lanthanum element of the periodic table.
• I in the chemical formula is Li, Mg, Ca, Sr, Ba, Be, Zn, Cd or Hg.
• ⁇ in the chemical formula is a ⁇ , IVA, VA, IVB or VB group element of the periodic table, or Sc or Y, or the like.
• ⁇ in the chemical formula is (, Ge, Sn, Ti, Hf, Mo, Zr, Al, W, Bi, B, Sc, Ga, In or Y, or the like.
• hydrazine in the chemical formula is a lanthanoid element or the like.
• III in the chemical formula is Eu, Ce, Mn, Sm, La, Pr or Tb or the like.
• x is from 0 to 1, most preferably 1;
• y is from 0 to 1, most preferably 1;
• z is from 0 to 1.1, preferably from 0 to 0.85, more preferably from 0 to 0.7, still more preferably from 0.007 to 0.5, most preferably from 0.007 to 0.25;
• w is 0 to 1, preferably 0 to 0.5, more preferably 0 to 0.3, still more preferably 0.03 to 0.3, most preferably 0.05 to 0.3.
• the nitride phosphor is excited by ultraviolet, near-ultraviolet or blue LED, and the emission wavelength is between 575 nm and 700 nm.
• the prepared nitride phosphor has a small particle size and does not require post-treatment polishing; 5.
• the prepared nitride phosphor has a high composition consistency;
• Fig. 1 is a spectrum diagram of Example 1 (excitation source is 460 nm).
• Fig. 2 is a SEM photograph of Example 1.
• Fig. 3 is a graph showing the particle size distribution of Example 1 and Comparative Example 1.
• the solid line in Fig. 3 is the particle size distribution of the sample obtained in Example 1, and the broken line is the particle size distribution of the sample obtained in Comparative Example 1.
• the method of the invention is carried out in accordance with the following steps:
• a reactive flux is added to the above raw materials, and the flux is used in an amount of 0.05% to 10% by mass of the phosphor.
• the mixture described in the step (4) is subjected to one or more heating synthesis by a solid phase reaction.
• the synthesis temperature of the solid phase reaction is 1200-1800 ° C, and the reaction time is 2-12 hours.
• the solid phase reaction is carried out under a reducing atmosphere, for example, a mixed gas of CH4/NH 3 as a reducing gas.
• the pressure of the solid phase reaction is 0.1-1.0 MPa.
• the phosphor material of the present invention is prepared.
• the phosphor material characterized in that the phosphor is excited by ultraviolet, near-ultraviolet or blue LED, and has an emission wavelength of between 575 and 700 nm.
• the nitride phosphor prepared by the present invention has an oxide atom which is uniformly distributed in combination with all constituent elements remaining in the product due to the use of an oxide as a raw material in the preparation. Through this side The oxygen atom distribution obtained by the method is significantly different from the oxygen atom obtained by mixing the oxide into the nitride. As a result of scanning electron microscopy analysis, in the conventional oxynitride-containing phosphor, the distribution of oxygen atoms is regional and cannot be uniformly dispersed throughout the system of the nitride phosphor. However, due to its source, the distribution of oxygen atoms in the nitride phosphor of the present invention and its uniformity do not have a distributional regionality throughout the nitride phosphor system.
• the nitride phosphor prepared by the method of the present invention has uniformity of oxygen atoms therein. The distribution brings about a higher color purity and better stability of the obtained emission spectrum of the phosphor.
• Nitrox analyzer HiROBA EMGA-920, from Horiba Group Ltd.
• the zirconium balls were separated, and the ethanol solvent was removed by centrifugation, and dried in a dry box at 120 degrees for 6 hours (the drying time was adjusted to 24 hours depending on the weight of the sample).
• a mixture of 5% (mass ratio, the same below) of CH4/NH 3 gas was heated for 2 hours for reduction roasting to obtain a nitride phosphor 1 . Its particle size distribution is shown by the solid line in FIG.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 12.528% and the nitrogen content was 18.9445%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, but the reduction baking time therein was changed to 3 hours to obtain a nitride phosphor 2.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 9.1507%, and the nitrogen content was 22.0293%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, but the reduction baking time therein was changed to 4 hours to obtain a nitride phosphor 3.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 5.7423%, and the nitrogen content was 25.1417%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, but the reduction baking time therein was changed to 6 hours to obtain a nitride phosphor 4.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.882%, and the nitrogen content was 27.7550%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that an 8% CH 4 /NH 3 mixed gas was passed, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 5.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.824%, and the nitrogen content was 27.7522%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, but a 12% CH 4 /NH 3 mixed gas was passed, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 6.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 28.825%, and the nitrogen content was 27.7549%. Calculated by the amount of raw material Other elemental content.
• Example 2 The same operation as in Example 1 was carried out, except that the calcination temperature therein was changed to 1500 °C, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 7.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.88222%, and the nitrogen content was 27.7542%.
• the other element content is calculated by the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that the calcination temperature was changed to 1600 °C, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 8.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.83232%, and the nitrogen content was 27.7548%.
• the other element content is calculated by the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that the calcination temperature therein was changed to 1800 °C, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 9.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.8826% and the nitrogen content was 27.7549%.
• the other element content is calculated by the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that 5.10 g of A1 2 0 3 was changed to 4.84 g of A1 2 0 3 , and 0.17 of 0 3 was added, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor. 10.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.9899%, and the nitrogen content was 27.9175%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that CaO was adjusted to 5.27 g, and 0.10 g of MgO was added, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 11.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.899%, and the nitrogen content was 27.9129%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, but CaO was adjusted to 4.21 g and added 3.54 g of SrC0 3 , the reduction calcination time was adjusted to 6 hours, and a nitride phosphor 12 was obtained.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.9688%, and the nitrogen content was 25.9746%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that CaO was adjusted to 3.08 g, and 6.49 g of SrCO 3 was added, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 13.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.5342%, and the nitrogen content was 24.4103%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that CaO was adjusted to 1.96 g, and 9.45 g of SrCO 3 was added, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 14.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.3901%, and the nitrogen content was 23.0220%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that CaO was adjusted to 0.84 g, and 12.40 g of SrCO 3 was added, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 15.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.2619%, and the nitrogen content was 21.7841%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that CaO was changed to 14.62 g of SrCO 3 and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 16.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.1526%, and the nitrogen content was 20.7511%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 18 The same operation as in Example 1 was carried out, except that 5.52 g of CaO was changed to 11.66 g of SrCO ⁇ P 3.94 g of BaCO 3 , and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 17 .
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.0433%, and the nitrogen content was 19.6728%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1, but in which CaO is replaced 5.52g 8.71g 7.89g of the SrC0 3 and BaC0 3, reduction roasting time was adjusted to 6 hours to obtain a nitride phosphor 18.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 2.2443%, and the nitrogen content was 21.6081%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that 5.52 g of CaO was changed to 5.76 g of SrCO ⁇ P ll.84 g of BaCO 3 , and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 19.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 1.8551%, and the nitrogen content was 17.8202%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, except that 5.52 g of CaO was changed to BaC0 3 of 19.54, and the reduction calcination time was adjusted to 6 hours to obtain a nitride phosphor 20.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and as a result, the oxygen content was 1.701%, and the nitrogen content was 16.3892%.
• the content of other elements was calculated from the amount of raw material charged.
• Example 2 The same operation as in Example 1 was carried out, and 25 mL of absolute ethanol was replaced with 25 mL of water to obtain a nitride phosphor 21.
• the nitrogen oxide content in the obtained phosphor was measured by nitrogen oxide analysis, and the result was an oxygen content of 2.8818% and a nitrogen content of 27.7540%.
• the content of other elements was calculated from the amount of raw material charged. Comparative example 1
• Example 1 As can be seen from the results in Table 1, by adjusting the reduction calcination time (Examples 1 to 4), the oxygen content in the phosphor was lowered, and the peak wavelength of the sample was also slightly blue-shifted (from 665 nm to 657 nm). The relative brightness was tested, and Examples 1 to 4 and Comparative Example 1 were 30%, 50%, 70%, and 100%, respectively. 99%, it can be seen that the oxygen content in the phosphor composition is optimally 0.25 mol.
• Example 1 In order to improve the reducing ability, Example 1, Example 5 and Example 6 adjusted the reducing atmosphere from 5%, 8% to 12%. After the completion of the calcination, it was found that a sample having a higher ratio (8% and 12%) of the reducing atmosphere showed black impurities, so that a reducing atmosphere of about 5% was preferable.
• the wavelengths of the phosphors can be adjusted by doping other elements and adjusting the ratio between the elements in Examples 10 to 20.
• the present invention can be used to produce phosphors having wavelengths from 575 nm to 700 nm. To adapt to different packaging requirements.
• the stability of the phosphor of the present invention was tested for packaging.
• the package mode is: Low Power Surface Mount LED (SMD LED), Specification: 5050.
• the encapsulation method is: weigh a certain amount of the phosphor of the embodiment or the comparative example of the invention (concentration in silica gel is 20%), uniformly disperse in the silicone resin (Dow Corning OE6630), and obtain the mixture after defoaming treatment.
• the mixture was coated on a blue LED chip (crystal chip, specification: 5050 RGB, emission wavelength 457.5-460 nm nm), and after heating at 80 ° C for 0.5 hour and 150 ° C for 2.5 hours, the package was completed.
• the stability value is the ratio of the measured luminous flux value to the initial luminous flux value after lighting for 2000 h.
• the stability test results showed that: 1) When the oxygen content in the phosphor was 0.25 mol (the phosphor of Example 4), the stability was the best (compared with the phosphor stability of Examples 1-3); 2) The stability data of Comparative Example 1 and Example 1 show that since the oxygen element is uniformly distributed in the phosphor of the present invention, it functions to stabilize the phosphor, and the phosphor prepared by the process of the present invention is prepared by the prior art. The phosphor is more stable. 3) By introducing other non-alkaline earth metal elements (phosphors of Examples 10 and 11) into the phosphor, the stability was slightly lowered.
• the invention discloses a method for preparing a nitride phosphor, which comprises the following steps: (a) a raw material mixing step, wherein a first raw material, a second raw material, a third raw material and a flux, or a first raw material, a third raw material and a flux, or a first raw material, Si 3 N 4 , a third raw material and a flux, or a first raw material, a second raw material, a third raw material, Si 3 N 4 and a flux added to the dispersing agent , uniformly mixing; (b) a drying step in which the uniformly mixed raw materials are dried; (c) a heating reduction step, wherein The dried mixed raw material is heated in a reducing gas.
• the present invention also relates to a nitride phosphor prepared by the method, the nitride phosphor having a chemical formula Where X is
• the method of the invention has the advantages that the raw material is cheap and easy to obtain, and the operation process is simplified.
• the prepared nitride phosphor has small particle size, narrow particle size distribution and high composition consistency, and the prepared nitride phosphor has oxygen atoms inherent in the starting material.
• the residue is such that oxygen atoms having extremely high dispersion and extremely uniform distribution are present in the prepared nitride phosphor, and the obtained phosphor emits a spectrum with higher color purity and better stability. Therefore, the method has good industrial applicability.

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• 2012
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